Bleachable light-absorbing layers for photography

ABSTRACT

QUINHYDRONE DYES ARE ADVANTAGEOUSLY INCORPORATED IN HYDROPHILIC COLLOID LAYERS OF PHOTOGRAPHIC ELEMENTS AS NONDIFFUSIBLE, BLEACHABLE DYES WHICH DO NOT REQUIRE MORDANTS.

United States Patent 3,565,627 BLEACHABLE LIGHT-ABSORBING LAYERS FOR PHOTOGRAPHY John A. Haefner and Herbert S. Wilgus III, Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Dec. 29, 1967, Ser. No. 694,379 Int. Cl. G03c 1/40, 1/100, 7/02 US. Cl. 9684 14 Claims ABSTRACT OF THE DISCLOSURE Quinhydrone dyes are advantageously incorporated in hydrophilic colloid layers of photographic elements as nondiffusible, bleachable dyes which do not require mordants.

This invention relates to photography including bleachable light-filtering hydrophilic colloid layers in which the bleachable dye is also a silver halide developing agent precursor, light-sensitive photographic elements containing the immediate lavers and processing of these lavers.

It is known that photographic elements require for many purposes to have light-screening substances incorporated therein. Such a light-screening substance may be in a layer overlying a light-sensitive emulsion or overlying two or more light-sensitive emulsions; or it may be in a light-sensitive emulsion for the purpose of modifying a light record in such emulsion or for protecting an overlying light-sensitive emulsion or emulsions from the action of light of wavelengths absorbed by such light-screening substance; or it may be in a layer not containing a lightsensitive substance but arranged between two light-sensitive emulsions; or it may be in a layer serving as a backing on an element having one or more light-sensitive emulsions (for example to reduce halation).

In particular, light-screening substances are often required (a) in overcoatings upon photographic elements to protect the light-sensitive emulsion or emulsions from the action of light which it is not desired to record, e.g., ultraviolet light in the case of still or moving pictures, especially color pictures, (b) in layers arranged between differentially color sensitized emulsions, e.g., to protect red and green sensitive emulsions from the action of blue light, and (c) in backings forming the so-called antihalation layers on either side of a transparent support carrying the light-sensitive emulsion or emulsions.

In most cases and especially where the element contains a color sensitized emulsion or color sensitized emul sions, it is particularly desirable to employ light-screening substances which do not effect the general sensitivity or the color sensitivity of light-sensitive emulsions with which they may come into contact. It is also particularly desirable to employ light-screening substances which do not substantially difiuse from the layers or coatings in which they are incorporated, either during the manufacture of the element or on storing it. Finally it is generally necessary to employ light-screening substances which can readily be rendered ineffective, i.e., decolorized or destroyed and removed prior to or during or after photographic processing. For many purposes it is particularly convenient to employ light-screening substances which are rendered ineifective by one of the photographic baths employed in processing the element after exposure, such as a photographic developing bath or fixing bath. The decoloration or destruction of the light-screening dye will hereinafter be referred to as bleaching.

Numerous dyes have been employed as light-screening materials for the purposes indicated above. In order to insure complete bleaching of the light absorbing dye during the normal photographic processing, the preferred dyes Patented Feb. 23, 1971 frequently have solubilized groups such as sulfonic acid or carboxylic acid groups which form diffusible watersoluble alkali metal salts during treatment with developer solutions. Because these dyes are difiusible, it is common practice to use basic mordants in the light-filtering layer to prevent these dyes from wandering, especially during the coating operation, from the light-filtering layer into adjacent layers where they are not wanted. Mordants tend to increase the thickness of the layers containing them and when used between image-forming layers the increased thickness tends to decrease image sharpness as well as the speed of image-forming layers coated under them. Layers containing mordants often have the very undesirable characteristic of mordanting components of the process solutions such as thiosulfate ions, etc., which are then retained in the processed film and eventually result in serious stain problems. Also under certain circumstances where the dye is not completely removed from the photographic element, the residual dye may be remordanted when the photographic element is made acid in a bath such as the stop bath or fixing solution.

It is known to incorporate developing agent precursors in photographic elements. Barr U.S. Pat. 3,295,978, issued J an. 3, 1967, for example, describes metal hydroquinone salts as developing agent precursors which are advantageously incorporated in layers of photographic elements. These colorless prior art developing agent precursors release active hydroquinone developing agents upon treatment with aqueous alkali and are advantageously used where no light filtering is needed.

Light filtering hydrophilic colloid layers that contain dyes that are nonditfusible Without the use of mordants but which are readily, completely and nonreversibly bleached during usual photographic development processes are desired. Light filtering hydrophilic colloid layers that contain in a single component a nonditfusible dye which upon treatment with aqueous alkali is bleached and simultaneously releases active silver halide developing agents are desired.

It is therefore an object of our invention to provide novel hydrophilic colloid layers containing as a nondiffusible dye a single component without a mordant which is not only readily bleached by alkaline processing solutions but releases silver halide developing agent.

It is another object of our invention to provide novel photographic elements containing our novel bleachable light-filtering layers which contain readily bleachable dyes which also serve as developing agent precursors and which are nondiifusible without being mordanted.

Still other objects and technical advances will be apparent from the following specification and claims.

These and other objects of our invention are achieved by providing water-permeable hydrophilic colloid layers containing our nondiffusible light-absorbing quinhydrone dyes that are nondiifusible without being mordanted and which are readily, completely and nonreversibly bleached and simultaneously release active silver halide developing agents by contacting with water having a pH greater than about 7.5 and preferably in the presence of a watersoluble sulfite (e.g. sodium sulfite, potassium sulfite, ammonium sulfite, etc.).

Our nonditfusible bleachable light-absorbing quinhydrone dyes used advantageously according to our invention included those having as the p-quinone moiety a compound represented by the formula:

wherein R represents hydrogen or the nonmetallic atoms which together with R represent the atoms necessary to complete a benzene ring (substituted or not), e.g., benzene, hydroxybenzene, nitrobenzene, cyanobenzene, sulfonic acid substituted benzene, carboxylic acid substituted benzene, alkyl substituted benzene in which the alkyl group has from 1 to 12 carbon atoms (e.g., methyl, ethyl, butyl, octyl, dodecyl, etc.), an alkoxy substituted benzene ring in which the alkoxy group has from 1 to 12 carbon atoms (e.g., methoxy, propoxy, decyloxy, dodecyloxy, etc.), an alkthio substituted benzene in which the alkthio group has from 1 to 12 carbon atoms (e.g., methylthio, propylthio, dodecylthio, etc.), an alkylcarbonyl substituted benzene in which the alkylcarbonyl group has from 1 to 12 carbon atoms (e.g., methylcarbonyl, ethylcarbonyl, hexylcarbonyl, dodecylcarbonyl, etc.), an alkenyl substituted benzene in which the alkenyl group has from 1 to 4 carbon atoms (e.g., allyl, crotyl, etc.), a halogen substituted benzene in which the halogen is chlorine, bromine, fluorine or iodine, an acyl substituted benzene in which the acyl group has from 1 to 12 carbon atoms (e.g., acetyl, butyryl, caprylyl, dodecanoyl, benzoyl, etc.), an acyloxy substituted benzene in which the acyloxy group has from 1 to 12 carbon atoms (e.g., acetoXy, benzoyloxy, decanoyloxy, etc.), etc.; R when R represents hydrogen, represents a member, such as hydrogen, hydroxyl, nitro, cyano,'the sulfonic acid group, the carboxylic acid group, an alkyl group having from 1 to 18 carbon atoms (e.g., methyl, carboxymethyl, ethyl, carboxyethyl, aminoethyl, N,N-diethylaminoethyl, N-morpholinoethyl, butyl, sulfobutyl, carboxyamyl, dodecyl, octadecyl, carboxyoctadecyl, etc.), an alkoxy group having from 1 to 18 carbon atoms (e.g., methoxy, propoxy, decyloxy, octadecyloxy, etc.), an alkthio group having from 1 to 18 carbon atoms (e.g., methylthio, butylthio, octylthio, octadecyl, etc.), an alkylcarbonyl group having from 1 to 19 carbon atoms (e.g., methylcarbonyl, butylcarbonyl, octylcarbonyl, octadecylcarbonyl, etc.), an alkenyl group having from 1 to 18 carbon atoms, (e.g., allyl, crotyl, etc.), a halogen atom (e.g., chlorine, bromine, fluorine, iodine), an acyl group having from 1 to 18 carbon atoms (e.g., acetyl, butyl, capryl, palmitoyl, benzoyl, etc.), an acyloxy group having from 1 to 18 carbon atoms (e.g., acetoxy, benzoyloxy, octadecyloxy, etc.), an aryl group, such as, a-naphthyl, fi-naphthyl and a phenyl group (e.g., phenyl, tolyl, carboxyphenyl, sulfophenyl, cyanophenyl, hydroxyphenyl, chlorophenyl, bromophenyl, iodophenyl, aminophenyl, etc.), an aryloxy group, such as, a naphthoxy group, a phenoxy group (e.g., phenoxy, tolyloxy, hydroxyphenoxy, chlorophenoxy, carboxyphenoxy, sulfophenoxy, etc.), an arylthio group, such as, a naphththio group and a phenylthio group (e.g., phenylthio, tolylthio, chlorophenylthio, carboxyphenylthio, hydroxyphenylthio, etc.), an amino group (e.g., amino, N,N-dimethylamino, N-phenylamino, etc.), a carbonyl group (e.g., carbamyl, N-ethylcarbamyl, N-methylcarbamyl, N-phenylcarbamyl, etc.), an alkylcarbonamido group (e.g., ethylcarbonamido, propylcarbonamido, etc.), an arylcarbonamido group (e.g., phenylcarbonamido, tolylcarbonamido, etc.), a sulfamyl group (e.g., sulfamyl, N-methylsulfamyl, N-propylsulfamyl, etc.), an alkylsulfonamido group (e.g., ethylsulfonamido, propylsulfonamido, etc.), and an arylsulfonamido group, particularly a phenylsulfonamido group (e.g., phenylsulfonamido, tolylsulfonamido, etc.); R and R each represent the same or diiferent member, such as, hydrogen, hydroxyl, nitro, cyano, the sulfonic acid group, the carboxylic acid group, an alkyl group having from 1 to 18 carbon atoms (e.g., methyl, carboxymethyl, ethyl, carboxyethyl, aminoethyl, N,N-diethylaminoethyl, N-morphilinoethyl, butyl, sulfobutyl, carboxyamyl, dodecyl, octadecyl, carboxyoctadecyl, etc.), an alkoXy group having from 1 to 18 carbon atoms (e.g., methoxy, propoxy, decyloxy, octadecyloxy, etc.), an alkthio group having from 1 to 18 carbon atoms (e.g., methylthio, butylthio, octylthio,

octadecyl, etc.), an alkylcarbonyl group having from 1 to 19 carbon atoms (e.g., methylcarbonyl, butylcarbonyl, octylcarbonyl, octadecylcarbonyl, etc.), an alkenyl group having from 1 to 18 carbon atoms, (e.g., allyl, crotyl, etc.), a halogen atom (e.g., chlorine, bromine, fluorine, iodine), an acyl group having from 1 to 18 carbon atoms (e.g., acetyl, butyl, capryl, palmitoyl, benzoyl, etc.), an acyloxy group having from 1 to 18 carbon atoms (e.g., acetoxy, benzoyloxy, octadecyloxy, etc.), an aryl group, such as, u-naphthyl, fl-naphthyl and a phenyl group (e.g., phenyl, tolyl, carboxyphenyl, sulfophenyl, cyanophenyl, hydroxyphenyl, chlorophenyl, bromophenyl, iodophenyl, aminophenyl, etc.), an arloxy group, such as, a naphthoxy group, a phenoxy group (e.g., phenoxy, tolyloxy, hydroxyphenoxy, chlorophenoxy, carboxyphenoxy, sulfophenoxy, etc.), an arylthio group, such as, a naphththio group and a phenylthio group (e.g., phenylthio, tolylthio, chlorophenylthio, carboxyphenylthio, hydroxyphenylthio, etc.), an amino group (e.g., amino, N,N-dimethylamino, N-phenylamino, etc.), a carbamyl group (e.g., carbamyl, N carbamyl, N ethylcarbamyl, N methylcarbamyl, N-phenylcarbamyl, etc.), an alkylcarbonamido group (e.g., ethylcarbonamido, propylcarbonamido, etc.), an arylcarbonamido group (e.g., phenylcarbonamido, tolylcarbonamido, etc.), a sulfamyl group (e.g., sulfamyl, N-methylsulfamyl, N-propylsulfamyl, etc.), an alkylsulfonamido group (e.g., ethylsulfonamido, propylsulfonamido, etc.), and an arylsulfonamido group, particularly a phenylsulfonamido group (e.g., phenylsulfonamido, tolylsulfonamido, etc.), and having as the dihydroxybenzene moiety a compound represented by the formula:

wherein R represents hydrogen or the nonmetallic atoms which together with R represent the atoms necessary to complete a benzene ring (substituted or not), e.g., benzene, hydroxybenzene, nitrobenzene, cyanobenzene, sulfonic acid substituted benzene, carboxylic acid substituted benzene, alkyl substituted benzene in which the alkyl group has from 1 to 12 carbon atoms (e.g., methyl, ethyl, butyl, octyl, dodecyl, etc.), an alkoxy substituted benzene ring in which the alkoxy group has from 1 to 12 carbon atoms (e.g., methoxy, propoxy, decyloxy, dodecyloxy, etc.), an alkthio substituted benzene in which the alkthio group has from 1 to 12 carbon atoms (e.g., methylthio, propylthio, dodecylthio,'etc.), an alkylcarbonyl substituted benzene in which the alkylcarbonyl group has from 1 to 12 carbon atoms (e.g., methylcarbonyl, ethyl carbonyl, hexylcarbonyl, dodecylcarbonyl, etc.), an alkenyl substituted benzene in which the alkenyl group has from 1 to 4 carbon atoms (e.g., alloyl, crotyl, etc.), halogen substituted benzene in which the halogen is chlorine, bromine, fluorine or iodine, an acyl substituted benzene in which the acyl group has from 1 to 12 carbon atoms (e.g., acetyl, butyryl, caprylyl, dodecanoyl, benzoyl, etc.), an acyloxy substituted benzene in which the acyloxy group has from 1 to 12 carbon atoms (e.g., acetoXy, benzoyloxy, decanoyloxy, etc.), etc.; R when R represents hydrogen, represents a member, such as hydrogen, hydroxyl, nitro, cyano, the sulfonic acid group, the carboxylic acid group, an alkyl group having from 1 to 18 carbon atoms (e.g., methyl, carboxymethyl, ethyl, carboxyethyl, aminoethyl, N,N-diethylaminoethyl, N-morpholinoethyl, butyl, sulfobutyl, carboxyamyl, dodecyl, octadecyl, carboxyoctadecyl, etc.), an alkoxy group having from 1 to 18 carbon atoms (e.g., methoxy, propoxy, decyloxy, octadecyloxy, etc.), an alkthio group having from 1 to 18 carbon atoms (e.g., methylthio, butylthio, octylthio, octadecyl, etc.), an alkylcarbonyl group having from 1 to 19 carbon atoms (e.g., methylcarbonyl, butylcarbonyl, octylcarbonyl, octadecylcarbonyl, etc.), an alkenyl group having from 1 to 18 carbon atoms (e.g., allyl, crotyl, etc.), a halogen atom (e.g., chlorine, bromine, fluorine, iodine), an acyl group having from 1 to 18 carbon atoms (e.g., acetyl, butyl, capryl, palmitoyl, benzoyl, etc.), an acyloxy group having from 1 to 18 carbon atoms (e.g., acetoxy, benzoyloxy, octadecyloxy, etc.), an aryl group, such as, a-naphthyl, B-naphthyl and a phenyl group e.g., phenyl, tolyl, carboxyphenyl, sulfophenyl, cyanophenyl, hydroxyphenyl, chlorophenyl, bromophenyl, idophenyl, aminophenyl, etc.), an aryloxy group, such as, a naphthoxy group, a phenoxy group e.g., phenoxy, tolyloxy, hydroxyphenoxy, chlorophenoxy, carbophenoxy, sulfophenoxy, etc.), an arylthio group, such as, a naphthio group and a phenylthio group e.g., phenylthio, tolylthio, chlorophenylthio, carboxyphenylthio, hydroxyphenylthio, etc.), an amino group e.g., amino, N,N-dimethylamino, N-phenylamino, etc.), a carbamyl group e.g., carbamyl, N-ethylcarbamyl, N-methylcarbamyl, N-phenylcarbamyl, etc.), an alkylcarbonamido group (e.g., ethylcarbonamido, propylcarbonamido, etc.), an arylcarbonamido group (e.g., phenylcarbonamido, tolylcarbonamido, etc.), a sulfamyl group (e.g., sulfamyl, N-methylsulfamyl, N-propylsulfamyl, etc.), an alkylsulfonamido group (e.g., ethylsul fonamido, propylsulfonamido, etc.), and an arylsulfonamido group, particularly a phenylsulfonamido group (e.g., phenylsulfonamido, tolylsulfonamido, etc.); R and 'R7 each represent the same or diflerent member, such as, hydrogen, hydroxyl, nitro, cyano, the sulfonica acid group, the carboxylic acid group, an alkyl group having from 1 to 18 carbon atoms (e.g., methyl, carboxymethyl, ethyl, carboxyethyl, aminoethyl-N,N-diethylaminoethyl, N-morpholinoethl, butyl, sulfobutyl, carboxyamyl, dodecyl, octadecyl, carboxyoctadecyl, etc.), an alkoxy group having from 1 to 18 carbon atoms (e.g., methoxy, proproxy, decyloxy, octadecyloxy, etc.), an alkthio group having from 1 to 18 carbon atoms (e.g., methylthio, butylthio, octylthio, octadecyl, etc.), an alkylcarbonyl group having from 1 to 19 carbon atoms (e.g., rnethylcarbonyl, butylcarbonyl, octylcarbonyl, octadecylcarbonyl, etc.), an alkenyl group having from 1 to 18 carbon atoms, (e.g., allyl, crotyl, etc.), a halogen atom (e.g., chlorine, bromine, fluorine, iodine), an acyl group having from 1 to 18 carbon atoms (e.g., acetyl, butyl, capryl, palmitoyl, benzoyl, etc.), an acyloxy group having from 1 to 18 carbon atoms (e.g., acetoxy, benzoyloxy, octadecyloxy, etc.), an aryl group, such as, a-naphthyl, fi-naphthyl and a phenyl group (e.g., phenyl, tolyl, carboxyphenyl, sulfophenyl, cyanophenyl, hydroxyl phenyl, chlorophenyl, bromophenyl, iodophenyl, aminophenyl, etc.), an aryloxy group, such as, a naphthoxy group, a phenoxy group (e.g., phenoxy, tolyloxy, hydroxyphenoxy, chlorophenoxy, carboxyphenoxy, sulfophenoxy, etc.), an arylthio group, such as, a naphthio group and a phenylthio group (e.g., phenylthio, tolylthio, chlorophenylthio, carboxyphenylthio, hydroxyphenylthio, etc.), an amino group (e.g., amino, N,N-dimethylamino, N-phenylamino, etc.), a carbamyl group (e.g., carbamyl, N-ethylcarbamyl, N-methylcarbamyl, N- phenylcarbamyl, etc.), an alkylcarbonamido group (e.g., ethylcarbonamido, propylcarbonamido, etc.), an arylcarbonamido group (e.g., phenylcarbonamido, tolylcarbon amido, etc.), a sulfamyl group (e.g., sulfarnyl, Nmethylsulfamyl, N-propylsulfamyl, etc.), an alkylsulfonamido group (e.g. ethylsulfonamido, propylsulfonamido, etc.), and an arylsulfonarnido group, particularly a phenylsulfonamido grou (e.g., phenylsulfonamido, tolylsulfonamido, etc.).

The exact structure of quinhydrones is not known, however, they are believed to be a complex formed in which one molecule of a hydroquinone is bonded to one molecule of a quinone. For purposes of cnvenience, we have described our quinhydrones by describing the structures of the quinone moiety and the hydroquinone moiety making up the quinhydrone molecule.

Examples of quinhydrones used to advantage according to our invention include those listed below described by the hydroquinone and quinone from which they are formed. For convenience, only substituents on the hydroquinone or p-quinone are tabulated except in those names bearing an asterisk which are the complete name of the hydroquinone or p-quinone.

Quin- Color of hydrone quin- Number Hydroquinone p-Quinone hydroue Zinethyl-Mrheira- Z-methyI-S-n-hexa- Blue.

deeyl. decyl. 2,5di-11-oetyl 2,5-di-n-octyl Do. do 2,5-di-n-nonyl Do. 2-u-lauryl-5-n-amyl. 2-n-lauryl-5-u-am yl. D0. 2,5-di-n-lauryl 2,5-di-n-lauryl Do. n-oetadecyl 2,5-di-n-octyl Purple. 2,5 di-n-oetyl Z-methyl-S-n-hexa- Blue.

decyl. n-octadecyl do Purple. Zn-lauryl-n-nmyl. Di-n-lauryl Bluev Methyl 2-i(rirethyl-5n-hexa- Do.

ee Isopropyl 2-methyl-5-n-hexa- Blue.

D p-Chlorophenyl Red ecy magenta. do p-Nitrophenylnuuu Green.

2-ehloro-6-tert-butyl- 2,5-diacetoxy Blue. o ll.. 2,3- Do. 2,5ditert-amyl .Z-methyl-in-hexa- Do.

decyl. 2,5-di-tert-0etyl d0 Do. 1,2,4,5-tetrahydroxy- Do.

benzene.* Trirnethyl Do. 2-allyl-5tert-buty Do. N (2-aminoethyl)- D0.

gentisamide.* 27 1,2,4,5-tetrahydroxy- 2,5-diaeetoxy Do.

benzenef 28 Trimethyl "do D0. 29 4,4-dimethyl-2,2,5,5- 3,4di-p-chlorophenyL Do.

tetrahydroxybiphenyl.* 30 Q-methyl-fi-n-hexa- 1,4naphthoquinone* Red.

decyl. 31 Phcuyl Purple.

2,5-di-n-nonyl Do. Do. Do. D0. D0. 2,5-di41-n0nyl. Do. n-Lauryl Do. 2,5-di-n-0ctyl Do. n-OctadeeyL Do. n-Octylun. D0. 2,5 di-n-lauiy D0. Q-nJauryl-fi-n-ar Do. 2 5-di-n-nonyl- Do. 2,5-cli-n-octyl Do. n-Octadecyl. Do. 1i-0etyl Do. ladi-tert-amyl Do. Tetrameth Do. 2-n-laury1-5-n-a1nyl Do. 2,5-di-n nonyl D0. n-Lauryl Do. 2,5-di-n- Do. n-Octadecyl D0. 2-11-lauryl-5-n-amyL Do. do 2,5-di-n-lauryl Do. uryl-5-na1nyl Do. Do. Do. Do. Do. Do. Do. Do. D0. Do. Do. D0. Tetramethyl Do. 2-n-lam-yl-5-n-a111yl Do. 11- aur Do. n-Oetadeeyl. Do. n-Octyl Do. 2,5di-r1laury Do. 2,5 '-11-oetyl Do. n-Octadecy D0. n-Octyl Do.

Quin- Color of hydrone quin- Number Hydroquinone p-Quinono hydrone 2,5-di-n-butyl 1...- 2,5-di-n-lauryl Blue do 2-n-lauryl-5-n-a1nyl. Do. do .1.... 2,5-di-n-nonyl Do. 4-phenylcatocho1* 2-methyl-5-n-l1oxa- Do.

decyl. Pyrogallol* -do Do. 2-methyl5-n-hexa- .do Black.

decyl plus Z-mcthyl- 5-n-palmityl. 4'y-carb0xyphenyl 4y-carboxyphcnyl. Blueblack. 2-phenyl do Do. 2(w-carboxypropyD- 2(m-carboxyamyl)-5- D0.

5-octyl. 5-0 2-(m-carboxyamyD-5- 2-(w-carboXyamyl) 5- D0.

methyl. methyl 94 d 2,5-di('y-carboxy- D0.

propyl 95 2-(y-carboxypropyl)-5 (2-(w-carboxyamy1)-5- Do.

octyl. methyl. 96 2-(y-suliopropyD-5- .do

octyloxy. 97 2-(N,N-diethylami11o- 2-(N,N-diethylaminoethylamino)-- ethylamino) -5- methyl. moth 98 6-carboxyl,4 5-carb0xy-2-hydroxy.

naphthohydroquinonc". 99 7-methyl-1A-naptho- 2-ctliyltl1i0-6-n1ethyl hydroquinone". 100. 2-ethylcarbonyl 2-ethylcarbonyl 101. 2-acetyl 2-acetyl 102 2-benzoyloxy 2l)enz0yloxy.. 103 2-phenylthi0 2-phenylthio L 2allyl-5-mothyl 2-allyl-5-mothyl 2-bromo-5-sull0 2-bromo-5-cyano Z-phenoxy-B-carbamyl. 2-phenoxy-3-earbam l. 2-phenylcarbonyl 2-pl1enylcarb0nyl 2-ethylcarb0narnido Z-phenylcarbonamido 2sulfamyl-3-methyl Z-SulfamyLIi-methyl.-- .1 2-othylsulfonamido 2-ethylsulfonamido 111 2-phenylsulfonamido 2-phenylsulfonamido These and still other quinhydrones of our invention are incorporated to advantage in Water-permeable hydrophilic colloids for use as bleachable light-absorbing filter layers and antihalation layers of photographic elements. The wide range of colors as well as black provided by quinhydrones makes them valuable for use in light-absorbing layers (either light-sensitive or not light-senstive) for absorbing light for various parts of the visible spectrum.

In general, our quinhydrones are prepared by mixing a solution of the p-quinone compound of Formula I and a solution containing an equimolar amount of the hydroquinone compound of Formula II and evaporating the resulting solution to dryness. Any suitable solvent, such as, methanol, ethanol, propanol, acetone, tetrahydrofuran, benzene, acetonitrile, ethyl acetate, methylene chloride, chloroform, carbon tetrachloride, hexane, cyclohexane, acetic acid, lower dialkyl ethers having less than about 7 total carbon atoms, and mixtures of two or more of these solvents are used to advantage. In those instances where the quinhydrone is not formed upon evaporation of the solvent from the solution, the quinhydrone is formed advantageously by heating the mixture of the compounds of Formula I and Formula II until one or both compounds melt usually at temperatures in the range from about C. to about 125 C. i

The specific preparation of typical quinhydrones will further serve to illustrate our invention.

The quinhydrone of Example 90 is advantageously prepared by adding to an acetone solution of 2.30 g. of 4'- carboxyphenylhydroquinone, an acetone solution of 2.28 g. of 4-carboxyphenylquinone and evaporating the solution to dryness at 40 C. leaving 4.52 g. of blue-black colored quinhydrone.

Similar procedures are used advantageously to prepare the other quinhydrones, however, it is necessary to heat the dried mixture of the appropriate compounds of Formula I and of Formula II to a temperature in the range from about 40 C. to 125 C. to make quinhydrone numbers 1 through 89.

The dihydroxybenzene compounds of Formula II are advantageously prepared according to methods well known in the art, and described in references including Loria et al. U.S. Pat. 2,728,659, Thirtle et al. U.S. Pat. 2,732,300,

Crevling et al. US. Pat. 2,899,334, etc. Many of these compounds are available. The p-quinone compounds of Formula I are prepared by oxidation of the corresponding dihydroxybenzene compounds. Suitable oxidizing agents comprise a mixture of sodium chlorate and vanadium pentoxide, dichromic acid, etc., as is illustrated in Cervling et al. U.S. Pat. 2,899,334.

The solid quinhydrones of our invention are advantageously reduced to a particle size in the range from about 0.1 to about 10 by any suitable method including, for example, ball-milling a mixtureof the quinhydrone and water. The dispersion of the quinhydrone in water is then intimately blended into an aqueous dispersion of the hydrophilic colloid that is to be used in our light-filtering layer. The resulting dispersion of our quinhydrone in the hydrophilic colloid is then coated on the photographic element or on its support, by methods well known in the art. Coating aids, such as, saponin are advantageously added to the dispersion prior to coating.

Hydrophilic colloidal materials used as binders include gelatin, collodion, gumarabic, cellulose ester derivatives such as akyl esters of carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, carboxy methyl hydroxy ethyl cellulose, synthetic resins, such as the amphoteric copolymers described by Clavier et al. in US. Pat. 2,949,442, issued Aug. 16, 1960, polyvinyl alcohol, and others well known in the art. The above-mentioned amphoteric copolymers are made by polymerizing the monomer having the formula:

CH =CR COOII wherein R represents an atom of hydrogen or a methyl group, and a salt of a compound having the general formula:

CHzNI-Iz wherein R has the above-mentioned meaning, such as an allylamine salt. These monomers can further be polymerized with a third unsaturated monomer in an amount of 0 to 20% of the total monomer used, such as an ethylene monomer that is copolymerizable with the two principal monomers. The third monomer may contain neither a basic group nor an acid group and may, for example, be vinyl acetate, vinyl chloride, acrylonitrile, methacrylonitrile styrene, acrylates, methacrylate, acrylamide, methacrylamide, etc. Examples of these polymeric gelatin substitutes are copolymers of allylamine and methacrylic acid; copolymers of allylamine, acrylic acid and acryamide; hydrolyzed copolymers of allylamine, methacrylic acid and vinyl acetate; copolymers of allylamine, acrylic acid and styrene; the copoymer of allyamine, methacrylic acid and acrylonitrile; etc.

The proportions of quinhydrone, colloidal binder and coating aid used in making our light-filtering layers can be varied over wide ranges and will depend upon the specific requirements of the photographic element being produced. The methods used to determine the optimum compositions are Well known in the art and need not be described here.

Hardening materials that may be used to advantage include such hardening agents as formaldehyde; a halogensubstituted aliphatic acid such as mucobromic acid as described in White, US. Pat. 2,080,019, issued May 11, 1937; a compound having a plurality of acid anhydride groups such as 7,8diphenylbicyclo (2,2,2)-7-octene-2,3,5, 6-tetra-carboxylic dianhydride, or a dicarboxylic or a disulfonic acid chloride such as terephthaloyl chloride or naphthalene-1,5-disulfonyl chloride as described in Allen and Carroll, US. Pat. 2,725,294 and 2,725,295, both issued Nov. 29, 1955; a cyclic 1,2-diketone such as cyclopentane- 1,2-dione as described in Allen Byers, U.S. Pat. 2,725,305, issued Nov. 29, 1955; a bi-ester of methane-sulfonic acid such as 1,2-di(methaneulfonoxy)-ethane as described in Allen and Laakso, US. Pat. 2,726,162, issued Dec. 6,

1955; 1,3-dihydroxymethylbenzimidazol-2-one as described in July, Knott and Pollak, US. Pat. 2,732,316, issued I an. 24, 1956; a dialdehyde or a sodium bisulfite derivative thereo, the aldehyde groups of which are separated by 2-3 carbon atoms, such as ,B-methyl glutaraldehyde bis-sodium bisulfite as described in Allen and Burness Canadian Pat. 588,451, issued Dec. 8, 1959; a bis-aziridine carboxamide such as trimethylene bis(1-aziridine carboxamide) as describedin Allen and Webster US. Pat. 2,950,- 197, issued Aug. 23, 1960; or 2,3-dihydroxydioxane as described in Ieffreys, US. Pat. 2,870,013, issued J an. 29,

The photographic element utilizing our light-screening layers have light-sensitive emulsion layers containing silver chloride, silver bromide, silver chlorobromide, silver iodide, slver bromoiodide, silver chlorobromoiodide, etc., as the light-sensitive material. Any light-sensitive silver halide emulsion layers may be used in these photographic elements. The silver halide emulsion may be sensitized by any of the sensitizers commonly used to produce the desired sensitometric characteristics.

Any other addenda used in light-filtering layers of photographic elements are used to advantage in our lightfiltering layers.

The light-sensitive layer or layers and our light-filtering layer or layers of our photographic element are coated advantageously on any suitable support material used in photography including glass, cellulose nitrate, cellulose acetate. synthetic resin, paper, etc.

Photographic elements containing our light-filtering layers are irreversibly bleached during treatment with alkaline solutions, such as, conventional photographic developer solutions. Upon contact with the alkaline solution the colored quinhydrone compound is destroyed releasing the quinone and dihydroxybenzene compound from which the quinhydrone was formed. The alkali metal salt of the dihydroxybenzene compound diffuses from the light-filtering layer and will develop light-exposed silver halide in an emulsion layer coated on the same side of the support, i.e., over or under the light-filtering layer. If desired, this developing agent released from the quinhydrone compound will serve as the sole developing agent in the development process or it can be used along with a second developing agent incorporated in the photographic element or in the developing solution to aid in photo graphic development. Sulfite ion present in conventional developer solutions forms a colorless salt of the faint yellowish-colored quinone compound released when the quinhydrone compound is destroyed. The alkali metal salt of the dihydroxy-benzene compound which is not used up in reduction of the latent image in silver halide to a silver image diffuses out of the photographic element 'during the photographic processing.

The following examples will still further illustrate our invention.

EXAMPLE 1 A mixture of 4.27 g. of quinhydrone number 90 and 60 ml. of water are ball-milled for 24 hours to give a dispersion of the quinhydrone having a particle size of La. A dispersion of 200 ml. total volume containing 3.5% gelatin and 2.00 g. of the ball-milled quinhydrone is coated on a cellulose acetate film base at 6.4 g./ft. resulting a coating containing 224 mg. gelatine/ft. and 64 mg. quinhydrone number 90/ft. The coating has a transmission density of 0.46. This layer is overcoated with a photographic hydrophilic colloid silver halide emulsion. The quinhydrone number 90 in this photographic element is bleached in 10 seconds to the transmission density of the film base by treatment with the following solutions: Kodak Developers D-19, D-76, DK50, and also 9% sodium sulfite, 5% sodium carbonate, and 9% sodium sulfite, and 5% sodium bicarbonate and 9% sodium sulfite. A 10-second and a -second treatment with 5% sodium carbonate both give a transmission density of 0.06. Treatment of pieces of the element with a 5% sodium bicarbonate solution in 30 seconds and 60 seconds gives transmission densities of 0.08 and 0.045, respectively.

EXAMPLE 2 Example 1 is repeated using quinhydrones number 91, 92, 93, 94, and separately in place of quinhydrone number 90. In each instance the quinhydrones in the coated photographic elements are bleached by treatment with the solutions in from about 10 to about 60 seconds as is found in Example 1.

Similar results are obtained when photographic elements are made incorporating our light-filtering layer either over or under a light-sensitive layer in a photographic element using quinhydrones formed from the quinones of Formula I and dihydroxy-benzene compounds of Formula II, including the quinhydrones 1 through 111 described above.

The following examples will show how the dihydroxybenzene compound released upon bleaching one of our quinhydrones will serve as the sole developing agent in a photographic process.

EXAMPLE 3 A 2.29 g. portion of quinhydrone number 90 is ballmilled for 24 hours in 40 ml. of water. The slurry is made up to ml. with water and 23 ml. of this is mixed with 25 g. of 10% gelatin and 2 ml. of water. Prior to coating, 05 ml. of a 15.3% saponin solution is added. A hand coating of 9.4 g./ft. is made on a cellulose acetate film base. This gives a quinhydrone concentration which will decompose to release 50 mg. of 4'-carboxy-phenylhydroquinone/ft? This layer is overcoated with a silver halide emulsion to give a silver concentration of 75 mg./ft. A solution is prepared corresponding to Kodak Developer D-19 without any p-methylaminophenol and Without any hydroquinone. A piece of the photographic element is exposed to a step tablet and developed with this solution for 20 minutes by sandwiching the film between two glass plates and using just enough solution to maintain a wet film. It is then washed one minute in Water, fixed four minutes in Kodak Fixing Agent F-5, and washed eight minutes to give 24 steps of silver density. As a control, a strip exposed and developed six minutes in Kodak Developer DK-SO, washed and fixed as above gives 26 steps of silver density.

EXAMPLE 4 Example 3 is repeated using quinhydrones number 91, 92, 93, 94, 95, 96 and 97 separately in place of quinhydrone number 90. Results similar to those in Example 3 are obtained with each of these quinhydrones.

It is to be understood that the preceding examples are illustrative and are not to limit the invention. Any of the hydrophilic colloids either with or without light-sensitive silver halide used in photographic layers are used to advantage as the binder in our light-filtering layers in place of gelatin.

Our photographic elements provide a number of technical advances. As mentioned previously, our quinhydrones are non-diffusible and will stay in the layer in which they are coated without any mordant, however, the dye is readily, completely and irreversibly bleached by treatment with the usual photographic developer solutions and simultaneously releases an active silver halide developing agent. Since our photographic elements do not contain any mordants, they can be thinner and will not retain thiosulfate ion and other processing chemicals which over a period of time decompose in the processed film with very detrimental and even disasterous results to the photographic quality. Our photographic elements are particularly valuable because not only is the incorporated dye component of the light-filtering layer an excellent bleachable dye that does not require a mordant but the dye is also an excellent silver halide developing agent precursor. Thus, the incorporation of a single component can serve the purpose of two and even three compounds 1 l (dye, developing agent precursor and mordant) required in prior art elements.

The invention has been described in detail with particular embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. A photographic element comprising a support coated with at least one water-permeable hydrophilic colloid layer containing light-sensitive silver halide and at least one water-permeable hydrophilic colloid layer containing a nonditfusible bleachable light-absorbing quinhydrone dye.

2. A photographic element comprising a support coated with at least one water-permeable hydrophilic colloid layer containing light-sensitive silver halide and at least one Water-permeable hydrophilic colloid layer containing a nondiffusible "bleachable light-absorbing quinhydrone dye having as the p-quinone moietry a compound selected from those having the formula:

wherein R represents a member selected from the class consisting of hydrogen and the nonmetallic atoms which together with R represent the atoms necessary to complete a benzene ring; R when R represents hydrogen, represents a member selected from the class consisting of hydrogen, hydroxyl, nitro, cyano, the sulfonic acid group, the carboxylic acid group, an alkyl group, an alkoxy group, an alkthio group, an alkylcarbonyl group, an alkenyl group, a halogen atom, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an arylthio group, an arylcarbonyl group, an amino group, a carbamyl group, an alkylcarbonamido group, an arylcarbonamido group, a sulfamyl group, an alkylsulfonamindo group, and an arylsulfonamido group; R and R each represent a member selected from the class consisting of hydrogen, hydroxyl, nitro, cyano, the sulfonic acid group, the carboxylic acid group, an alkyl group, an alkoxy group, an alkthio group, an alkylcarbonyl group, an alkenyl group, a halogen atom, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an arylthio group, an arylcarbonyl group, an amino group, a carbamyl group, an alkylcarbonamido group, an arylcarbonamido group, a sulfamyl group, an alkylsulfonamido group, and an arylsulfonamido group; and having as the dihydroxy benzene moiety 8. compound selected from those having the formula:

C JH

wherein R represents a member selected from the class consisting of hydrogen and the nonmetallic atoms which together with R represent the atoms necessary to complete a benzene ring; R when R represents hydrogen, represents a member selected from the class consisting of hydrogen, hydroxyl, nitro, cyano, the sulfonic acid group, the carboxylic acid group, an alkyl group, an alkoxy group, an alkthio group, an alkylcarbonyl group, an alkneyl group, a halogen atom, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an arylthio group, an arylcarbonyl group, an amino group, a carbamyl group, an alkylcarbonamido group, an arylcarbonamido group, a sulfamyl group, an alkylsulfonamido group, and an arylsulfonamido group; R and R each represent a member selected from the class consisting of hydrogen, hydroxyl, nitro, cyano, the sulfonic acid group, the carboxylic acid group, an alkyl group, an alkoxy group, an alkthio group, an alkylcarbonyl group, an alkenyl group, a halogen atom, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an arylthio group, an arylcarbonyl group, an amino group, a carbamyl group, an alkylcarbonamido group, an arylcarbonamido group, a sulfamyl group, an alkylsulfonamido group, and an arylsulfonamido group.

3. A photographic element of claim 2 in which the layer containing the bleachable quinhydrone dye is coated between the support and the layer containing light-sensitive silver halide.

4. A photographic element comprising a support coated with at least one water-permeable hydrophilic colloid layer containing light-sensitive silver halide and at least one water-permeable hydrophilic colloid layer containing a nonditfusible bleachable light-absorbing quinhydrone dye having as the p-quinone moiety a compound selected from those having the formula:

wherein R represents a member selected from the class consisting of hydrogen and the nonmetallic atoms which together with R represent the atoms necessary to complete a benzene ring; R when R represents hydrogen, represents a member selected from the class consisting of hydrogen, a carboxylalkyl group having from 1 to 19 carbon atoms and a carboxyphenyl group; R and R each represent a member selected from the class conisting of hydrogen, hydroxyl, nitro cyano, the sulfonic acid group, the carboxylic acid group, an alkyl group, an alkoxy group, an alkthio group, an alkylcarbonyl group, .an alkenyl group, a halogen atom, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an arylthio group, an arylcarbonyl group, an amino group, a carbamyl group, an alkylcarbonamido group, an arylcarbonamido group, a sulfamyl group, an alkylsulfonamido group, and an arylsulfonamido group; and having as the dihydroxy benzene moiety a compound selected from those having the formula:

wherein R represents a member selected from the class consisting of hydrogen and the nonmetallic atoms which together with R represent the atoms necessary to complete a benzene ring; R when R represents hydrogen, represents a member selected from the class consisting of hydrogen, a carboxyalkyl group having from 1 to 19 carbon atoms and a carboxyphenyl group; R and R each represent a member selected from the class consisting of hydrogen, hydroxyl, nitro, cyano, the sulfonic acid group, the carboxylic acid group, an alkyl group, an alkoxy group, an alkthio group, an alkylcarbonyl group, an alkenyl group, a halogen atom, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an arylthio group, an arylcarbonyl group, an amino group, a carbamyl group, an alkylcarbonamido group, an arylcarbonamido group, a sulfamyl group, an alkylsulfonamido group, and an arylsulfonamido group.

5. A photographic element of claim 4 in which the said hydrophilic colloid is gelatin and the said quinhydroquinone has a 4'carboxyphenyl quinone moiety and a 4- carboxyphenyl hydroquinone moiety.

6. A photographic element of claim 4 in which the said hydrophilic colloid is gelatin and the said quinhydroquinone has a 4-carboxyphenyl quinone moiety and a phenyl hydroquinone moiety.

7. A photographic element of claim 4 in which the said hydrophilic colloid is gelatin and the said quinhydroquinone has a 2-(w-carboxyamyl)-5-octyl quinone and a 2-('y-carboxypropyl)-5-octyl hydroquinone moiety.

8. A photographic element of claim 4 in which the said hydrophilic colloid is gelatin and the said uinhydroquinone has a 2-(w-carboxyamyl)-5-methyl quinone moiety and a 2-(w-carbOXyamyD-S-methyl hydroquinone moiety.

9. A photographic element of claim 4 in which the said hydrophilic colloid is gelatin and the said quinhydroquinone has a 2,5-di-('y-carboxypropynquinone moiety and a 2-(w-carbOXyamyD-S-methyl hydroquinone moiety.

10. A photographic element of claim 4 in which the said hydrophilic colloid is gelatin and the said quinhydroquinone has a 2-(w-sulfoamyl)-5-methyl quinone moiety and a 2-(y-sulfopropyl)-5-octyloxy hydroquinone moiety.

11. A photographic element of claim 4 in which the said hydrophilic colloid is gelatin and the said quinhydroquinone has a 2-(N,N-diethylarninoethyl)-5-methyl quinone moiety and a 2-(N,N-diethylarninoethyl)-5-methyl hydroquinone moiety.

12. A photographic element of claim 4 in which the said hydrophilic colloid is gelatin and the said quinhydroquinone has a 2-(w-carboxyamyl)-5-methyl quinone miety and a 2-( -carboxypropyl)-5-octyl hydroquinone moiety.

13. A photographic element of claim 2 in which the said bleachable quinhydrone dye is in the said hydrophilic colloid layer containing light-sensitized silver halide.

14. A process for simultaneously developing a silver image and bleaching a filter dye in a light-image-exposed photographic element, said element comprising a support coated with at least one water-permeable hydrophilic colloid layer containing light-image-exposed light-sensitive silver halide and at least one water-permeable hydrophilic colloid layer containing a nondiffusible bleachable lightabsorbing quinhydrone dye, said process comprising the step of contacting the said element with water having a pH above about 7.5 and containing a water-soluble sulfite.

References Cited UNITED STATES PATENTS 3,036,914 5/1962 Jennings 9684 3,330,656 7/1967 Schuler 9684X 3,368,900 2/1968 Metucher 96--1 15 3,406,069 10/1968 Overman 9684X 3,427,161 2/1969 Laridon 96-1 15X 3,457,074 7/1969 Wilson et al 9699 WILLIAM D. MARTIN, Primary Examiner W. R. TRENOR, Assistant Examiner US. Cl. X.R. 

